Azo dyestuffs



Patented Feb. 27, 1940 UNITED STATES PATENT OFFICE 2,192,153 AZO DYESTUFFS Hans Roos, Leverkusen-I. G.-Werk, Rhine, Ger- -many, assignor to General Aniline-8; Film Corporation, a corporation of Delaware No Drawing. Application September 1, 1938, Se-

r-ial No. 227,969.

4 Claims.

In this formula Xcstands for a CClinkage (diphenyl linkage) or for the -CH=CHbridg-e; R and R1 are benzene nuclei which may besubstituted at most by a methyl group, Y stands-for hydrogen or any substituent as for instance alkyl, halogen, SO3H, the nitro group, theacylamino group or amino group andtheresidue N= N'-R,

' B being the radical of acouplingcompouent and at least one of the nuclei designated A contains a good dischargeability. If thev starting compoe nents contain a nitro or an acylamino group these groups may be converted into free amino groups by reduction or saponification. The aminodisazo dyestuifs thus obtained as well as the nitro or acylamino dyestuffs from which-they 5 have been prepared are as suchof technical importance; these dyestuffs can be further diazotized in substance or, after the dyeing, on the fiber and coupled with any coupling component for azo dyestufis. If these coupling components are properly chosen the good dischargeability previously present can be retained. As coupling components may be mentioned, for example, salicyclic acid, pyrazolones, resorcinol or its 45 monoazo dyestufis whichmay contain also metal;

I naphthol sulfonic acids, aminonaphithol sulfonic acids and the derivatives thereof as well as their monoazo dyestuffs as far as they arecapab-le" of coupling a second time, and many others. In 50 order .to obtain dyestuffs which contain in the initial component an acylamino group it is often useful to carry out theacylation-only in the dyestuffs; thus this acylation can be carried through also e. g. in the above mentioned aminodisazo 5'5' dyestufis. Chiefiy benzoylation, treatment with In Germany September 8,

phosgene and cyanuric chloride are best carried out in this stage.

The following examples illustrate the invention, without, however, restricting it thereto, the parts 7 being by weight.

' Example 1 38.6 parts of monoacetyl-benzidine-3l3-disulionic acid are diazotized with sodium nitrite and hydrochloric acid in the usual manner and com- 19 bined with 11 parts of m-toluidine in acetic solution, The separated monoazodyestuff is further diazotized with a slight excess of sodium nitrite and hydrochloric acid and then coupled with 9 parts of phenol in sodium carbonate alkaline 15 medium. 'I heseparated 'dyestufi which is sensitiveit'oalka'li" is alkylated' with methylchlorid'e in a:5.0% alcoholic solution'at' 90400 0. in" the usual manner. The dyestufi dyes cotton yelloworange shades and the 'dyeings are distinguished by a very goodjfastness to light and a good discharge ability both in neutral and alkaline medium. It corresponds in the free state to the following formula:

CH: 7 I

tows

If this dyestufi' issaponified by heatingit for one hour in a dilute sodium hydroxide solution to 90 C. a product is obtained of similar tinctorial properties as the unsaponified dyestuff, dyeingcotton somewhat redder orange shadesz S-OtH scan S0311 sour ,I'n contradistinction to the unsaponified dye- 40 dyes cotton clear orange shades of good dissponds in the free state to the following formula:

' 2,192,153 chargeability and fastness to light. It correstuff is done away with by alkylation with methyl chloride at 90 C.

b5 C.OH

If, in this example, as coupling component, 23 parts of 1- (3'-amino) -phenyl-5-pyrazolone-3- carboxylic acid are used, a dyestuff is obtained which dyes cotton the same shade. The dyeing can be further diazotized on the fiber and developed with B-naphthol or pyrazo-lone to an orange of good fastness to light and good dischargee ability. Also by aftertreatment with diazotized p-nitroaniline on the fiber an orange crown of good fastness to washing is obtained which is likewise distinguished by a good fastness to light and good dischargeability.

If in this example instead of the pyrazolones 2-amino-B-hydroxynaphthalene-G-sulfonic acid is used as coupling component a full brown is obtained which can be deepened by further diazotizin-g and coupling with m-phenylene diamine in substance or on the fiber,

Bluish brown shades are obtained by. employing as coupling component (coupling to be carried out in alkaline medium) the monoazo dyestufi prepared by coupling diazotized o-chloranilinesulfonic acid with 2-amino-5-hydroxynapthalene- SOQH Example 3 parts of 4-nitro-4'-aminostilbene-2.2'-disulfonic acid are diazotized with 7 parts of sodium nitrite and hydrochloric acid in the usual manner and run into a hydrochloric solution of 11 parts of m-toluidine. By gradually adding sodium acetate the coupling become complete and the monoazo dyestuff is isolated. It is diazotized with sodium nitrite and hydrochloric acid in the usual manner. The diazo compound is filtered off and coupled with phenol in sodium carbonate alkaline solution. The sensitiveness toalkali of this dye- The dyestufi thus 'obtainedcorresponds in the free state to the following formula.

mN-QGEECH-QmN-QI I NOD 0H:

S 03H SOsH and dyes cotton very clear orange shades; it is distinguished by a good fastness to light and a good dischargeability both in alkaline and neutral medium. g

A very similar dyestuff is obtained by starting from 4-aminostilbene- 22-disulfonic acid instead from 4 nitro-4'-aminostilbene 2.2- disulfonic acid. 1

By reducing the nitro-dyestuff with sodium sulfide. at 60 C. a dyestufiis obtained which dyes cotton brown shades, also of good dischargeis obtained, which dyes cotton clear orange shades fast to light and well dischargeable. A very similar product is obtained if instead of acetic anhydride benzoyl chloride is used for the acyla tion. The dyestuff thus obtained is distinguished by a somewhat improved fastness to water.

By treating the above described aminodisazo dyestufi with p-nitrobenzoylchloride at 70 C. and reducing the separated condensation product with sodium sulfide a dyestuff is obtained which corresponds in the free state to the following formula:

and which likewise dyes cotton orange shades;

The dyeing can be developed onthe fiber, e. g. with p-naphthol to a red clause of good fastness to light, very good fastness to washing and good dischargeability.

Example 4 S0311 SOaH' 60.1 parts ofthe dyestuff prepared according to. Example 3 which corresponds to the above formula are diazotized in exactly the same manner as the dyestufi of Example 2 and also coupled in the same manner with different coupling components. Thus dyestuffs are obtained ofsimilar properties, but dyeing different shades, e. g. with I 1-phenyl-5-pyrazolonee3-carboxylic acid a well dischargeable scarlet is obtained. Also with l-(3-an1inophenyl) -5-.pyrazolone 3 .carboxylic S'O H If in the preceding examples instead of phenol 0- or m-cresol is used for the final coupling,

' dyestuffs are" obtainedwhich practically do not differ from the corresponding dyestuffs containing phenol.

HQN

I claim:

. 1. As new products azo dyestuffs of the general formula:

' l Z Z wherein X stands for one of the group consisting m-toluidine aniline-o of the diphenyl linkage and the --CI-I==CH-- bridge, Y stands for one of the group consisting of hydrogen, alkyl, halogen, the sulfonic acid group, the nitro group, the acyl-amino group, the azo-pyrazolone group and the amino group capable of being diaz'otized and of coupling, Z stands for one of the group consisting of hydrogen and methyl and at least one of the nuclei cle fignated A contains a sulfonic acid group.

2. As new products azo dyestuffs of the general formula:

wherein X stands for one of the group consisting of the diphenyl linkage andthe CH=C H- bridge, Y stands for'one' of the groupconsist- 1.

ing of hydrogen, alkyl, halogen the sulfonic acid group, the nitro group, the acyl amino group, the azo-pyrazolone group and the amino group capable of being diazotized and of coupling and Z stands for one of the group consisting of hydrogen and methyl.

3. As new product the azo dyestufi corresponding in its free state to the formula:

OCH:

dyeing cotton clear orange shadesof good fastness to light and good dischargeability.

4. As new product the azo dyestu'fi corresponding in its free state to the formula:

dyeing cotton clear orange shades of good fastness to light and good dischargeability, changing to orange brown shades of good fastness to light and washing and of good dischargeability when aftertreated on the fiber with diazotized p-nitraniline. I

HANS ROOS. 

